CN109956503B - NiMoS for supercapacitor electrode material4Preparation method of (1) - Google Patents

NiMoS for supercapacitor electrode material4Preparation method of (1) Download PDF

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CN109956503B
CN109956503B CN201910209226.5A CN201910209226A CN109956503B CN 109956503 B CN109956503 B CN 109956503B CN 201910209226 A CN201910209226 A CN 201910209226A CN 109956503 B CN109956503 B CN 109956503B
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nimos
electrode material
preparation
tetrathiomolybdate
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CN109956503A (en
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徐晓阳
刘倩倩
魏婷
张向京
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Hebei University of Science and Technology
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Hebei University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention provides a NiMoS for an electrode material of a super capacitor4The method of (2), which comprises: s1 dissolving Ni source in deionized water and stirring to obtain Ni-containing solution2+A solution A of ions; s2, adding tetrathiomolybdate, morphology regulator and acid-base regulator into deionized water, stirring and dissolving to prepare the product containing MoS4 2‑A solution B of ions; s3, slowly dripping 1 volume of the solution A into 2 volumes of the solution B within 0.5 hour, and stirring and mixing to obtain a mixed solution C; s4, heating the mixed solution C at 30-90 ℃ for 2-10 hours, and carrying out chemical precipitation reaction; s5, cooling the product to room temperature after the chemical precipitation reaction is finished, washing and drying to obtain NiMoS4. NiMoS of the invention4The preparation method can lead the prepared product NiMoS to be regulated and controlled in the reaction process4Has a lamellar structure, so that the electrode material of the super capacitor capable of improving specific capacitance can be obtained.

Description

NiMoS for supercapacitor electrode material4Preparation method of (1)
Technical Field
The invention relates to the technical field of preparation of electrode materials of capacitors, in particular to NiMoS for an electrode material of a super capacitor4The preparation method of (1).
Background
The performance of the super capacitor as a novel high-efficiency clean energy storage device mainly depends on electrode materials. At present, transition metal oxides or sulfides are reported to be used as electrode materials of supercapacitors, and transition metal sulfides have higher specific capacitance and conductivity than corresponding oxides, so that the transition metal sulfides are concerned in the field of electrode materials of supercapacitors due to good performance of the transition metal sulfides.
In order to make up for the deficiency of the properties of the monometallic compound and to fully utilize the advantages of the electrochemical properties of various metal atoms, the bimetallic sulfide has been paid more and more attention by researchers because it can exhibit better electrochemical properties than the corresponding monometallic sulfide. However, when the bimetallic sulfide which is reported in the prior art is used as an electrode material of a supercapacitor, the specific capacitance value of the bimetallic sulfide is still low and needs to be improved.
Disclosure of Invention
In view of the above, the present invention is directed to a NiMoS for an electrode material of a super capacitor4The method of (2) to obtain an electrode material that can have a higher specific capacitance.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
NiMoS for supercapacitor electrode material4The preparation method comprises the following steps:
s1 dissolving Ni source in deionized water and stirring to obtain Ni-containing solution2+A solution A of ions;
s2, adding tetrathiomolybdate, morphology regulator and acid-base regulator into deionized water, stirring and dissolving to prepare the product containing MoS4 2-A solution B of ions;
s3, slowly dripping 1 volume of the solution A into 2 volumes of the solution B within 0.5 hour, and stirring and mixing to obtain a mixed solution C;
s4, heating the mixed solution C at 30-90 ℃ for 2-10 hours, and carrying out chemical precipitation reaction;
s5, cooling the product to room temperature after the chemical precipitation reaction is finished, washing and drying to obtain NiMoS4。
Further, Ni in solution A2+The concentration of the ions is 0.05mol/L, and MoS in the solution B4 2-The concentrations of the ion and the morphology regulator are respectively 0.025mol/L, and the concentration of the acid-base regulator is 0.0025 mol/L.
Further, the nickel source is one of nickel nitrate hexahydrate and nickel chloride hexahydrate.
Further, the tetrathiomolybdate is one of sodium tetrathiomolybdate, potassium tetrathiomolybdate and ammonium tetrathiomolybdate.
Further, the morphology regulator is one of cetyl trimethyl ammonium bromide, sodium dodecyl sulfate, hexamethylene tetramine and ammonium fluoride.
Further, the pH regulator is sodium citrate.
Further, the heating in step s4 is water bath heating, and the washing in step s5 is 2 times of washing with 10 times of the volume of the product of deionized water and absolute ethyl alcohol in sequence.
Further, the drying in step s5 is drying for 10h in a vacuum drying oven with a temperature of 40 ℃ and an absolute pressure of 5 kPa.
Compared with the prior art, the invention has the following advantages:
the invention relates to NiMoS for an electrode material of a super capacitor4The preparation method reduces the surface tension by regulating and controlling the reaction process and adding the appearance regulator, the oleophylic group forms steric hindrance on the particle surface, the agglomeration of nano particles is prevented, and the prepared product NiMoS can be prepared4Has the morphology characteristic of a lamellar structure, so that the NiMoS prepared by the lamellar structure can be used4The formed electrode material has larger specific surface area, and further, the electrode material of the super capacitor capable of improving specific capacitance can be obtained.
Also, the NiMoS of the present invention4The preparation method has the advantages of simple preparation process, controllable reaction conditions and simpler preparation device, and is favorable for popularization and application in the field of super-capacitor electrode materials.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows a preparation example in the example of the present invention1 NiMoS prepared4Scanning electron microscope pictures;
FIG. 2 is a graph of NiMoS prepared in preparation example 1 according to the present invention4Transmission electron microscope pictures.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The embodiment relates to NiMoS for an electrode material of a super capacitor4The method comprises dissolving a nickel source in deionized water and stirring to prepare Ni-containing2+Adding tetrathiomolybdate, a morphology regulator and an acid-base regulator into deionized water, stirring and dissolving to prepare a solution A containing MoS4 2-Slowly dripping 1 volume of the solution A into 2 volumes of the solution B within 0.5 hour, stirring and mixing to obtain a mixed solution C, heating the mixed solution C at 30-90 ℃ for 2-10 hours to perform chemical precipitation reaction, cooling the product to room temperature after the chemical precipitation reaction is finished, washing and drying to obtain NiMoS4。
Wherein Ni is contained in the solution A in the preparation method2+The concentration of the ions is 0.05mol/L, and MoS in the solution B4 2-The concentrations of the ion and the morphology regulator are respectively 0.025mol/L, and the concentration of the acid-base regulator is 0.0025 mol/L. And, the nickel source is nickel nitrate hexahydrate (Ni (NO)3)2·6H2O), nickel chloride hexahydrate (NiCl)2·6H2O), tetrathiomolybdate is sodium tetrathiomolybdate (Na)2MoS4) Potassium tetrathiomolybdate (K)2MoS4) Ammonium tetrathiomolybdate ((NH)4)2MoS4) The morphology regulator is one of cetyl trimethyl ammonium bromide, sodium dodecyl sulfate, hexamethylene tetramine and ammonium fluoride. The pH regulator is sodium citrate.
Furthermore, the stirring operation in the above preparation method preferably adopts magnetic stirring, the washing specifically adopts deionized water and absolute ethyl alcohol with 10 times of the volume of the product to wash for 2 times respectively, and the subsequent drying is drying for 10 hours in a vacuum drying oven with the temperature of 40 ℃ and the absolute pressure of 5 kPa.
The NiMoS of this example is further illustrated below in particular by several preparation examples4And (4) preparing.
Preparation of example 1
NiMoS of this example4In the preparation of the electrode material, nickel chloride hexahydrate (NiCl) is firstly mixed2·6H2O) is dissolved in deionized water and stirred to prepare Ni2+Solution A with the ion concentration of 0.05mol/L is taken and ammonium tetrathiomolybdate ((NH)4)2MoS4) Hexamethylene tetramine and sodium citrate are added into deionized water to be stirred and dissolved to prepare solution B, and MoS in the solution B4 2-The concentration of ions and hexamethylene tetramine is 0.025mol/L respectively, and the concentration of sodium citrate is 0.0025 mol/L.
Then, 1 volume of solution A was slowly added dropwise to 2 volumes of solution B over 0.5 hour, and stirred and mixed to obtain mixed solution C, which was heated in a water bath at 90 ℃ for 6 hours to perform a chemical precipitation reaction. Cooling the resultant to room temperature after the precipitation reaction is finished, respectively centrifugally washing the obtained product for 2 times by using deionized water and absolute ethyl alcohol, and drying the product for 10 hours in a vacuum drying oven at the temperature of 40 ℃ and the absolute pressure of 5kPa to obtain the black electrode material NiMoS4。
NiMoS electrode material prepared in this example4The scanning electron microscope and the transmission electron microscope pictures are respectively shown in figure 1 and figure 2, and the electrode material NiMoS4In a three-electrode system, a specific capacitance value of 730F/g is reached in a voltage range of 0-0.5V and a current density of 0.5A/g through a constant current charge-discharge (GCD) electrochemical test in 1mol/L KOH electrolyte.
Preparation of example 2
NiMoS of this example4In the preparation of the electrode material, nickel nitrate hexahydrate (Ni (NO) is first mixed3)2·6H2O) is dissolved in deionized water and stirred to prepare Ni2+Solution A with the ion concentration of 0.05mol/L is taken and ammonium tetrathiomolybdate ((NH)4)2MoS4) Cetyl trimethyl ammonium bromide (CT)AB) and sodium citrate are added into deionized water to be stirred and dissolved to prepare solution B, and MoS in the solution B4 2-The concentrations of the ions and the cetyl trimethyl ammonium bromide are respectively 0.025mol/L and the concentration of the sodium citrate is 0.0025 mol/L.
Then, 1 volume of solution A was slowly added dropwise to 2 volumes of solution B over 0.5 hour, and stirred and mixed to obtain mixed solution C, which was heated in a water bath at 60 ℃ for 2 hours to perform a chemical precipitation reaction. Cooling the resultant to room temperature after the precipitation reaction is finished, respectively centrifugally washing the obtained product for 2 times by using deionized water and absolute ethyl alcohol, and drying the product for 10 hours in a vacuum drying oven at the temperature of 40 ℃ and the absolute pressure of 5kPa to obtain the black electrode material NiMoS4。
NiMoS electrode material prepared in this example4Through the same electrochemical test, the specific capacitance value reaches 525F/g under the current density of 0.5A/g.
Preparation of example 3
NiMoS of this example4In the preparation of the electrode material, nickel chloride hexahydrate (NiCl) is firstly mixed2·6H2O) is dissolved in deionized water and stirred to prepare Ni2+Solution A with the ion concentration of 0.05mol/L is taken and ammonium tetrathiomolybdate ((NH)4)2MoS4) Adding sodium dodecyl sulfate and sodium citrate into deionized water, stirring and dissolving to prepare solution B, wherein MoS in the solution B4 2-The concentration of the ions and the concentration of the sodium dodecyl sulfate are respectively 0.025mol/L, and the concentration of the sodium citrate is 0.0025 mol/L.
Then, 1 volume of solution A was slowly added dropwise to 2 volumes of solution B over 0.5 hour, and stirred and mixed to obtain mixed solution C, which was heated in a water bath at 100 ℃ for 10 hours to perform a chemical precipitation reaction. Cooling the resultant to room temperature after the precipitation reaction is finished, respectively centrifugally washing the obtained product for 2 times by using deionized water and absolute ethyl alcohol, and drying the product for 10 hours in a vacuum drying oven at the temperature of 40 ℃ and the absolute pressure of 5kPa to obtain the black electrode material NiMoS4。
NiMoS electrode material prepared in this example4By the same electrochemical test, at 0.5The specific capacitance value reaches 433F/g under the current density of A/g.
As can be seen from the above preparation examples, NiMoS obtained by the preparation method of this example4The specific capacitance value of the electrode material at the current density of 0.5A/g is between 433F/g and 730F/g, which is compared with the prior NiMoS4The electrode greatly improves the specific capacitance value.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (6)

1. NiMoS for supercapacitor electrode material4The preparation method is characterized by comprising the following steps: the method comprises the following steps:
s1 dissolving Ni source in deionized water and stirring to obtain Ni-containing solution2+A solution A of ions;
s2, adding tetrathiomolybdate, morphology regulator and acid-base regulator into deionized water, stirring and dissolving to prepare the product containing MoS4 2-A solution B of ions;
s3, slowly dripping 1 volume of the solution A into 2 volumes of the solution B within 0.5 hour, and stirring and mixing to obtain a mixed solution C;
s4, heating the mixed solution C at 30-90 ℃ for 2-10 hours, and carrying out chemical precipitation reaction;
s5, cooling the product to room temperature after the chemical precipitation reaction is finished, washing and drying to obtain NiMoS4；
Wherein the concentration of the morphology regulator in the solution B is 0.025mol/L, and the concentration of the acid-base regulator is 0.0025 mol/L; the shape regulator is one of cetyl trimethyl ammonium bromide, sodium dodecyl sulfate, hexamethylene tetramine and ammonium fluoride, and the acid-base regulator is sodium citrate.
2. NiMoS for supercapacitor electrode material according to claim 14The preparation method is characterized by comprising the following steps: solutions ofIn A Ni2+The concentration of the ions is 0.05mol/L, and MoS in the solution B4 2-The concentration of the ions was 0.025 mol/L.
3. NiMoS for supercapacitor electrode material according to claim 14The preparation method is characterized by comprising the following steps: the nickel source is one of nickel nitrate hexahydrate and nickel chloride hexahydrate.
4. NiMoS for supercapacitor electrode material according to claim 14The preparation method is characterized by comprising the following steps: the tetrathiomolybdate is one of sodium tetrathiomolybdate, potassium tetrathiomolybdate and ammonium tetrathiomolybdate.
5. NiMoS for supercapacitor electrode material according to any one of claims 1 to 44The preparation method is characterized by comprising the following steps: the heating in step s4 was water bath heating, and the washing in step s5 was 2 times of washing with deionized water and absolute ethanol each in a volume 10 times that of the product.
6. NiMoS for supercapacitor electrode material according to any one of claims 1 to 44The preparation method is characterized by comprising the following steps: the drying in step s5 is drying for 10h in a vacuum drying oven with a temperature of 40 ℃ and an absolute pressure of 5 kPa.
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CN110797203A (en) * 2019-09-29 2020-02-14 河北科技大学 Electrode material NiMoS for super capacitor4Preparation method of/RGO
CN110853931A (en) * 2019-11-01 2020-02-28 河北科技大学 Synthesis method of cobalt-molybdenum bimetallic sulfide for supercapacitor electrode material
CN112490019A (en) * 2020-12-09 2021-03-12 桂林电子科技大学 Polydopamine-coated MXene-based composite material and preparation method and application thereof

Non-Patent Citations (3)

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Controlled growth of NiMoO4 •H2O nanoflake and nanowire arrays on Ni foam for superior performance of asymmetric supercapacitors;Chen Qing,et al;《RSC Advances》;20160708;第6卷(第72期);67785-67793 *
Low-Cost and High-Performance CoMoS4 and NiMoS4 Counter Electrodes for Dye-Sensitized Solar Cells;Xiaojia Zheng，et al;《CHEMICAL COMMUNICATIONS》;20130823;第49卷(第83期);全文 *
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